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The procedure takes as input parameters the measured (or calculated) pKa and the measured (or calculated) octanol water partition coef cient, log P The latter parameter is used to estimate the intrinsic solubility S0, using the Hansch-type expression [38], log S0 1:17 1:38 log P, or an improved version for ionizable molecules of moderate lipophilicity (Fig 66): log S0 2:17 0:0082 log P 0:134 log P 2 6:13

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Using the pKa and the estimated S0 , the DTT procedure simulates the entire titration curve before the assay commences Figure 67 shows such a titration curve of propoxyphene The simulated curve serves as a template for the instrument to collect individual pH measurements in the course of the titration The pH domain containing precipitation is apparent from the simulation ( lled points in Fig 67) Titration of the sample suspension is done in the direction of dissolution (high to low pH in Fig 67), eventually well past the point of complete dissolution (pH < 73 in Fig 67) The rate of dissolution of the solid, described by the classical Noyes Whitney expression [37], depends on a number of factors, which the instrument takes into account For example, the instrument slows down the rate of pH data taking as the point of complete dissolution approaches, where the time needed to dissolve additional solid substantially increases (between pH 9 and 73 in Fig 67) Only after the precipitate completely dissolves, does the instrument collect the remainder of the data rapidly (un lled circles in Fig 67) Typically, 3 10 h is required for the entire equilibrium solubility data taking The more insoluble the

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